The invention relates to the improvement of the quality of polyalkylene polyamines prepared from an alkyleneamine compound and an alkanolamine compound.
Amination by ammonolysis relates to those reactions in which an amino compound is formed using ammonia or a primary or secondary amine as the amination agent.
Historically, ethylenediamine was prepared from ethylenedichloride using such type of reaction. The ethylenedichloride was treated in a pressure autoclave with aqueous ammonia at 100.degree. to 180.degree. C., with ethylenediamine and amine hydrogen chlorides resulting. A large excess of ammonia was used in order to favor the formation of the primary amine over the various secondary products; even then only a 40 percent yield of the desired product was obtained. The reaction was non-catalytic. In general, the product obtained after neutralization of the amine salts from the process, upon separation of the product from the sodium chloride and usual by-products using conventional separation techniques, such as, distillation, had a color similar to the color of pure ethylenediamine and only the normal slight ammoniacal odor of polyethylene amines prepared using ammonia. Pure ethylenediamine is a clear, colorless, liquid which has an ammonia odor.
The ethylene dichloride route has comparatively high capital investment requirements and comparatively high utility costs, plus a number of environmental problems associated with it. The environmental difficulties associated with the ethylene dichloride route include side reaction to vinyl chloride and disposal of sodium chloride contaminated with organics.
The art subsequently developed catalytic processes for producing polyalkylene polyamines from an alkyleneamine compound having at least two amino groups and an alkanolamine having at least one amino group. Some of the catalytic processes also had ammonia or a primary amine or a secondary amine present as a reactant.
U.S. Pat. No. 4,463,193 discloses a process for preparing predominantly noncyclic polyalkylene polyamines. Ammonia or a primary or secondary amine is contacted with an alkanolamine compound having an amino group and having a primary or secondary hydroxy group and an alkyleneamine compound having two amino groups in the presence of a catalytically effective amount of a Group IIIB metal acid phosphate. A temperature is used which is sufficient to effect a reaction among the ammonia or amine, the alkanolamine compound and the alkyleneamine compound under a pressure sufficient to maintain a substantial amount of the ammonia or amine in the reaction zone. The polyalkylene polyamines produced by U.S. Pat. No. 4,463,193 are often of poor quality, having a dominant burnt-scorched odor which is quite objectional and having a very dark black color. The black color has been measured as being a Gardner Color Standard Number of 20 to 40 on the Gardner Color Scale. Such poor quality polyalkylene polyamines are poorly accepted on a commercial basis by the art. The art wants and uses polyalkylene polyamines which are much ligher, almost white, in color and which do not have such malodors.
Polyalkylene polyamines produced from an alkyleneamine having at least two amino groups and an alkanolamine having at least one amino group in the presence of a phosphorus-containing catalyst, such as, a metal phosphate or a cation exchange resin containing active phosphortic sites sometimes are also of similar poor quality. The burnt-scorched odor and dark black color of such poor quality polyalkylene polyamines are commercially unacceptable by the art.
Catalytic processes for the preparation of polyalkylene polyamines from ethylene oxide and ammonia using a reductive amination catalyst, such as, nickel on a support, are generally not susceptible to the production of such poor quality polyalkylene polyamines.
The following are a number of patents which have hydrogen present in reactors using various reductive amination catalysts. Applicants do not make any express or implied representation that the following patents are pertinent to applicants' invention in a patentable sense.
U.S. Pat. No. 4,404,405 discloses a continuous process for the manufacture of polyethylene polyamines. A continuous homogeneous fluid stream under pressure which contains ammonia, monoethanolamine, diethanolamine and triethanolamine (as produced by the direct reaction of ethylene oxide and ammonia) is provided. The amination feed stream is supplied to the amination zone, which is maintained at a superatmospheric pressure but sufficiently below the pressure of the amination feed stream to assure flow thereof through the amination zone and to form an amination product from containing ethyleneamines therein. The preferred catalyst is a solid material comprising nickel and rhenium on a support. The amination feed stream can optionally contain water, hydrogen and/or ammonia. The hydrogen may be supplied to the reaction zone as a separate feed stream into the amination zone or as a component of the amination feed stream. The hydrogen serves the purpose of a promoter for the catalyst. When hydrogen is not provided in the reaction zone and the catalyst is a nickel-rhenium catalyst as described above, the catalyst life is greatly shortened and the rate of amine production is materially reduced. By providing hydrogen in the amination zone, the catalyst is continuously promoted to effectively cause the amination of the alkanolamines to produce the desired products. Patent '405 states that it is believed that hydrogen acts as a continuously supplied inert to keep available sites at the catalyst surface for the desired reaction between ammonia and the ethanolamines and to preclude the stabilization of the catalyst sites by alkyleneamines and/or ammonia. The amount of hydrogen that should be present in the amination feed stream should be from about one mole percent to about 30 mole percent based on the total moles in the amination feed stream.
U.S. Pat. No. 3,714,259 discloses preparing polyethylene polyamines by reacting an ethyleneamine and an ethanolamine in the presence of a hydrogenation catalyst and under hydrogen pressure of 200 to 5,000 p.s.i.g. The catalyst is composed of oxides or salts of nickel, copper, iron, palladium, platinum, cobalt, chromium, rhodium, molybdenum and titanium. Promoters such as bauxite, pumice and kieselguhr can be used in combination with the catalyst.
U.S. Pat. No. 4,123,462 discloses producing ethylenediamine by reacting monoethanolamine with ammonia in the presence of hydrogen and a supported nickel-rhenium catalyst. The amount of hydrogen present is not critical. The hydrogen is added in an amount sufficient to keep the catalyst in an active state.
U.S. Pat. No. 4,209,424 discloses a catalytic process in a heterogenous phase for producing ethylenediamine and piperazine from ethanolamine and ammonia. The ethanolamine-ammonia reaction in the presence of the amination catalyst is conducted at a temperature between 170.degree. and 260.degree. C. at a pressure between 50 and 300 bars absolute. The ethanolamine, ammonia, and hydrogen are introduced into the reactor in quantities such that the ammonia-ethanolamine molar ratio is between 5 and 40 and the hydrogen flow rate is between 5 and 200 ml per mole of ethanolamine. The amination catalyst has at least one active metal from the group of transition metals consisting of nickel, cobalt and copper, uniformly combined with a refractory microporous substance.
U.S. Pat. No. 4,153,581 discloses a method of producing amines by contacting at reactive conditions at least one alcohol, aldehyde or ketone, or a mixture thereof, with an aminating agent in the presence of a catalyst. The catalyst is composed of cobalt, copper and a third component selected from the group consisting of iron, zinc, zirconium and mixtures thereof. The aminating agent can be, for example, ethylenediamine, and the alcohol can be ethanolamine. The method generally employs hydrogen. The amount of hydrogen employed can vary according to convenience but a typical minimum hydrogen:alcohol mole ratio is at least about 0.1:1.
U.S. Pat. No. 4,111,840 discloses the catalytic amination of lower aliphatic alkane derivatives, such as, alkanols, alkanediols and alkanolamines, using a nickel-rhenium catalyst. Hydrogen can be used in the reactor, but the amount of hydrogen gas present is not critical. Usually, the addition of hydrogen is done in an amount sufficient to bring the reaction mixture to the desired reaction pressure.
U.S. Pat. No. 4,254,060 discloses the production of aliphatic amines by reacting an aliphatic alcohol or an aliphatic aldehyde, with ammonia or a primary or secondary amine, in the presence of a homogeneous colloidal catalyst prepared by reducing a mixture of components. The mixture includes an inner complex salt of copper or silver, a carboxylate of copper or silver, an inner complex salt or a carboxylate of an element of Group VIII of the Periodic Table of Elements, manganese or zinc, and a fatty acid or an alkali metal or alkaline earth metal carboxylate. Preferably, the reaction is carried out in the presence of a small amount of hydrogen because the amounts of by-products having a higher boiling point are reduced and the reaction time is reduced to some extent.
U.S. Pat. No. 4,322,530 discloses a process for alkylating a polyamine by contacting, in a liquid media, a polyamine, an olefinic compound, carbon monoxide, and a hydrogen source in the presence of a catalytic amount of a rhodium atom-containing compound at a temperature of from about 50.degree. to 250.degree. C. and at pressure of from 30 to 300 atmospheres. The source of hydrogen can be water. Hydrogen can be used with the water, but poorer yields are obtained.
U.S. Pat. No. 4,210,605 discloses preparing aliphatic amines by reacting an aliphatic alcohol or an aliphatic aldehyde with ammonia or a primary or secondary aliphatic amine, in the presence of a homogeneous colloidal catalyst prepared by reducing a copper or silver salt of a carboxylic acid. The reaction can proceed even in the absence of hydrogen. However, it is preferred that the reaction by carried out in the presence of a small amount of hydrogen, because formation of high-boiling-point substances is reduced and the reaction time can be shortened to some extent.
U.S. Pat. No. 3,766,184 discloses catalytically converting aliphatic alcohols and aminoalcohols, and mixtures of aliphatic alcohols and aminoalcohols to aliphatic and heterocyclic amines by reaction with ammonia. The reaction is carried out in the presence of hydrogen and in the presence of a catalyst composition consisting essentially of iron and nickel and/or cobalt. The reaction betweenw the ammonia and the alcohol is carried out with ammonia in the presence of hydrogen gas, in order to ensure a good yield of the desired aliphatic amine product. The hydrogen can reduce a catalyst initially present as the oxides to the elemental metals. Generally, the quantity of hydrogen gas required is relatively small, and corresponds to a proportion of from about 2 to about 30 percent. Higher proportions of hydrogen can be employed, but generally, however, without any noticable benefit.
U.S. Pat. No. 4,229,378 discloses producing tertiary amines by reacting aliphatic, cycloaliphatic or araliphatic alcohols, aldehydes or ketones with ammonia, primary or secondary amines in the presence of a catalyst which is a mixture of copper, tin and an alkali metal supported on a suitable carrier. The reaction is preferably conducted in the presence of hydrogen, using partial pressures of hydrogen of from about 10 p.s.i.g. to about 3000 p.s.i.g. The catalyst is a reduction catalyst; the hydrogen provides a reducing atmosphere.
U.S. Pat. No. 4,206,149 discloses producing amines by reacting alcohols, aldehydes or ketones with ammonia, primary or secondary amines in the presence of a catalyst which is a mixture of copper and rhenium. The reaction is also preferably conducted in the presence of hydrogen.
U.S. Pat. No. 2,349,461 discloses preparing lower aliphatic amines having at least two carbon atoms attached to the nitrogen atom, by reacting hydrogen with a mixture of a lower aliphatic nitrile and at least one lower aliphatic aldehyde. The reaction is carried out in the presence of a hydrogenating catalyst at a temperature within the range of 180.degree. to 400.degree. C. An excess of hydrogen can be used.
U.S. Pat. No. 4,014,933 discloses a process for the production of an amine by reacting an alkanol having one to eighteen carbon atoms, or a cycloalkanol having five to twelve carbon atoms, or an alkanolamine, with ammonia or a primary or secondary amine in the presence of hydrogen and a cobalt-nickel copper-containing aluminum oxide or silicon dioxide supported catalyst at a temperature of from 100.degree. C. to 200.degree. C. and at a pressure of 10 to 250 atmospheres. 5 to 100 liters of hydrogen can typically be used per mole of alcohol.
U.S. Pat. No. 4,409,399 discloses a process for producing aliphatic amines by reacting an aliphatic alcohol or an aliphatic aldehyde with an aminating agent, which is ammonia, a primary amine and a secondary amine, in the liquid phase in the presence of an unsupported catalyst. The catalyst contains copper oxide or copper hydroxide, nickel oxide or nickel hydroxide, and, optionally, an oxide or an hydroxide of a Group IIA metal. Before using the catalyst, it is activated by reducing with hydrogen, preferably while it is dispersed within the reactant alcohol or aldehyde. This can be done, for example, by passing hydrogen therethrough while maintaining a temperature of about 100.degree. to about 200.degree. C. over a period of about 15 minutes to about one hour at atmospheric pressure. In a preferred embodiment, the liquid alcohol or liquid aldehyde is charged to a stirred reaction vessel along with the desired catalyst mixture, after which the reaction vessel is purged with an inert gas, such as nitrogen. Then as the reaction vessel is heated to reaction temperature, the catalyst is activated by bubbling hydrogen into and through the liquid phase. When the desired reaction temperature has been reached, for example, in the range of about 150.degree. to about 300.degree. C. and the catalyst has been activated, a gas stream containing hydrogen and the reactant amine is passed through the reaction mixture.
The following patents are also of interest.
European Pat. No. 0,069,322 shows producing dimethylaminoethylmorpholine from morpholine and dimethylethanolamine in the presence of water and hydrogen at a temperature in the range of about 285.degree. to 420.degree. C., a pressure in the range of about 0.1 to 1.5 atmospheres, a liquid hourly space velocity of 0.05 to 1.5 in the presence of a catalyst which is a pyrophosphate, a monohydrogen phosphate or a dihydrogen phosphate of strontium, copper, magnesium, calcium, barium, lanthanum, or a mixture thereof.
U.S. Pat. No. 3,297,701 discloses producing diazabicyclo-(2.2.2)-octane and C-substitute diazabicyclo-(2.2.2)-octanes by contacting a metal phosphate catalyst with a piperazine compound, such as, N-hydroxyethylpiperazine. Examples of the metal phosphate catalysts include an aluminum phosphate, boron phosphate, iron phosphate, calcium phosphate, lithium phosphate, zinc phosphate, nickel phosphate, chromium phosphate, copper phosphate and cobalt phosphate. U.S. Pat. No. 3,297,701 states that hydrogen may also be employed in the process, for example, as a purge or carrier gas. Example XVII of U.S. Pat. No. 3,297,701 provided a 5 weight percent higher yield of ethyltriethylenediamine when hydrogen was used (at a space velocity of 3,440 cc./hr./cc./catalyst) than when no hydrogen was used.
U.S. Pat. No. 3,120,525 discloses the reaction of ammonia and an ethyleneic polyamine, such as, aminoethylpiperazine. The catalyst typically is a silica-alumina catalyst or a tungsten oxide catalyst. U.S. Pat. No. 3,120,525 states that, if desired, hydrogen can be added to the reactor, but no reason if given for the addition and the quantity to be added is not mentioned.